CN110049971A - Diamines, polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element - Google Patents

Diamines, polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element Download PDF

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CN110049971A
CN110049971A CN201780075183.5A CN201780075183A CN110049971A CN 110049971 A CN110049971 A CN 110049971A CN 201780075183 A CN201780075183 A CN 201780075183A CN 110049971 A CN110049971 A CN 110049971A
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liquid crystal
formula
polymer
diamines
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CN110049971B (en
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相马早纪
森本佳道
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)

Abstract

Make it with the diamines of structure shown in following formula [1].(in formula [1], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2It is each independently-H ,-OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3.In addition, any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.)

Description

Diamines, polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
Technical field
Indicated the present invention relates to new diamine, for liquid crystal the polymer of element, aligning agent for liquid crystal, liquid crystal orientation film, with And liquid crystal indicates element.
Background technique
Now, liquid crystal indicates that element is used as the display unit of PC, mobile phone, television receiver etc. extensively.Liquid crystal Indicate that element has the liquid crystal layer being for example clamped between device substrate and filter substrate, applies the pixel of electric field to liquid crystal layer Electrode and common electrode, the liquid crystal orientation film for controlling liquid crystal layer liquid crystal molecular orientation, to the electric signal for pixel electrode into The thin film transistor (TFT) (TFT) etc. of row switching.Wherein, liquid crystal orientation film be by will by polyimide precursor i.e. polyamic acid ( Referred to as " polyamic acid "), the polyimides system aligning agent for liquid crystal of its acid imide compound, that is, polyimides solution composition applies Cloth is formed a film on substrate and is made.
In recent years, liquid crystal indicates that high performance, the power saving larger in area, display device etc. of element are promoted, and And be used under various environment, characteristic required by liquid crystal orientation film is also further stringent.Therefore, by changing polyamic acid or gathering The various methods such as the dopant or additive of imido structure, addition characteristic different polyamic acid or polyimides, carry out Improvement, control of pre-tilt angle of liquid crystal aligning, electrical characteristics etc. etc..
As 1 example of the method for improving liquid crystal aligning membrane property, the tool used as polyamic acid raw material is proposed There is new structural diamines.For example, patent document 1 is disclosed containing derivative with new structural diamines and aliphatic tetrabasic carboxylic acid It is excellent and can reduce charge accumulation to be capable of providing voltage retention by using the aligning agent for liquid crystal for the aligning agent for liquid crystal of object Liquid crystal indicates element.
But the high performance of element is indicated along with liquid crystal, characteristic required by liquid crystal orientation film is also further stringent, only It is difficult to meet all requirement characteristics with conventional art.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2010/053128
Summary of the invention
Problems to be solved by the invention
In view of the foregoing, the purpose of the present invention is to provide for improve liquid crystal indicate element characteristic new diamine, Indicate that polymer, aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal of element indicate element for liquid crystal.
The solution to the problem
The inventors of the present invention are by further investigation, as a result, it has been found that liquid will be used for by using polymer obtained from specific diamines When crystalline substance indicates element, the flashing (flickering) for especially driving initial stage can be reduced, effectively so as to complete this hair It is bright.It should be noted that diamines of the invention described hereinafter is the new compound that existing technical literature is not recorded.
Diamines of the invention for achieving the above object, which is characterized in that indicated by following formula [1].
(in formula [1], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Each independently For-H ,-OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3.In addition, phenyl ring is appointed Meaning hydrogen atom is optionally replaced by 1 valence organic group.)
Polymer of the invention for achieving the above object, which is characterized in that it is by comprising with following formula [2] institute Show what the diamine component of the diamines of structure obtained.
(in formula [2], Y1For singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2It is each independently-H ,-OH ,=O or 1 Valence organic group, R3For the alkylidene of carbon atom number 1~3, * indicates the position with other group bondings.In addition, phenyl ring is any Hydrogen atom is optionally replaced by 1 valence organic group.)
In addition, above-mentioned polymer is preferably obtained as the diamine component comprising the diamines with structure shown in following formula [3].
(in formula [3], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Each independently For-H ,-OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3, * is indicated and other bases The position of group's bonding.In addition, any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.)
In addition, above-mentioned polymer be preferably selected from the polyimide precursor containing structural unit shown in following formula [4] and its At least one of imide compound, that is, polyimides.
(in formula [4], X1For the 4 valence organic groups from tetracarboxylic acid derivatives, W1For from formula [2] or formula [3] institute Show the divalent organic group of the diamines of structure.R5And R6Indicate the alkyl of hydrogen atom or carbon atom number 1~5, A1And A2It is respectively independent Ground indicates the alkynyl of hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~5 or carbon atom number 2~5.)
Aligning agent for liquid crystal of the invention for achieving the above object, which is characterized in that contain polymer and organic solvent.
Liquid crystal orientation film of the invention for achieving the above object, which is characterized in that it is by above-mentioned aligning agent for liquid crystal It obtains.
Liquid crystal of the invention for achieving the above object indicates element, which is characterized in that has above-mentioned liquid crystal orientation film.
The effect of invention
In accordance with the invention it is possible to which providing indicates the new diamine of element characteristic for improving liquid crystal, indicates member for liquid crystal Polymer, aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal of part indicate element.
Specific embodiment
In the following, the present invention is described in detail.
< diamines >
Diamines of the invention is indicated by following formula [1].
(in formula [1], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Each independently For-H ,-OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3.In addition, phenyl ring is appointed Meaning hydrogen atom is optionally replaced by 1 valence organic group.)
In formula [1], as 1 valence organic group, alkyl can be enumerated；Hydroxyl, carboxyl, hydroxyl, mercapto or carboxyl Alkyl；The alkyl connected by linking groups such as ehter bond, ester bond, amido bonds；Alkyl containing silicon atom；Halohydrocarbyl；Amino； The nonactive group etc. that amino is protected by the carbamate systems blocking group such as tert-butoxycarbonyl.It should be noted that alkyl It can be any one of straight chain, branch and closed chain, in addition, both can may be unsaturated hydrocarbons for saturated hydrocarbons.In addition, alkyl Part hydrogen atom optionally by carboxyl, hydroxyl, mercapto, silicon atom, halogen atom etc. replace, optionally pass through ehter bond, ester bond, amide The connection of the linking groups such as key.
In addition, the alkylidene of carbon atom number 1~3 can be any one of straight chain, branch and closed chain.Specifically, it can arrange Enumerate methylene, ethylidene, n-propylene, isopropylidene, ring propylidene, 1- methyl-ring propylidene, 2- methyl-ring propylidene, 1,1- dimethyl-n-propylene, 1,2- dimethyl-n-propylene, 2,2- dimethyl-n-propylene, 1- ethyl-n-propylene, 1,2- dimethyl-ring propylidene, 2,3- dimethyl-ring propylidene, 1- ethyl-ring propylidene, 2- ethyl-ring propylidene, 1,1, 2- trimethyl-n-propylene, 1,2,2- trimethyl-n-propylene, 1- ethyl -1- methyl-n-propylene, 1- Ethyl-2-Methyl - N-propylene, 2- n-propyl-ring propylidene, 1- isopropyl-ring propylidene, 2- isopropyl-ring propylidene, 1,2,2- trimethyl- Ring propylidene, 1,2,3- trimethyl-ring propylidene, 2,2,3- trimethyl-ring propylidene, 1- Ethyl-2-Methyl-ring propylidene, 2- ethyl -1- methyl-ring propylidene, 2- Ethyl-2-Methyl-ring propylidene and 2- ethyl -3- methyl-ring propylidene etc..
It should be noted that the alkylidene of 1 valence organic group, carbon atom number 1~3 can select various groups depending on the application.
As the specific example of diamines shown in formula [1], diamines shown in following formula [5-1]~formula [5-13] can be enumerated, but It is not limited only to this.
It should be noted that Boc indicates following shown groups (tert-butoxycarbonyl) in formula [5-3].
The synthetic method > of < diamines
In the following, being illustrated to the primary synthetic methods of diamines of the invention.It should be noted that method described below For synthesis example, it is not limited only to this.
As shown in following reaction equations, diamines of the invention can by reduction dinitro compound by nitro be converted to amino come It obtains.It should be noted that in following reaction equations, with phenyl ring and the hydrogen atom of saturated hydrocarbons part not by except halogen atoms such as fluorine atoms Or it is recorded for the diamines of the 1 valence organic group substitution other than amino.
(in above-mentioned reaction equation, Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Respectively solely It is on the spot-H ,-OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3.In addition, phenyl ring Any hydrogen atom optionally replaced by 1 valence organic group.)
The method of reduction dinitro compound is not particularly limited, and can exemplify using palladium-carbon, platinum oxide, Raney's nickel, platinum Black, rhodium-aluminium oxide, vulcanization platinum carbon etc. are used as catalyst, in ethyl acetate, toluene, tetrahydrofuran, dioxanes, alcohol system equal solvent In, the method that is restored by hydrogen, hydrazine, hydrogen chloride etc..Autoclave etc. can also be used as needed to carry out under elevated pressure.Separately On the one hand, when in the structure of the substituent group replaced to the hydrogen atom of phenyl ring, saturated hydrocarbons part including unsaturated bond position, if Using palladium carbon, platinum carbon etc., then the unsaturated bond position may be reduced, and become saturated bond, thus preferably using reduced iron or Reducing condition of the transition metal such as tin, stannic chloride as catalyst.
Above-mentioned reaction can carry out in the presence of base.About the alkali of use, do not limited especially as long as it can synthesize It is fixed, the inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium hydride, pyrrole can be enumerated Organic bases such as pyridine, dimethyl aminopyridine, trimethylamine, triethylamine, tri-n-butylamine etc..In addition, in some cases, and use dibenzylidene Whens palladium catalyst, copper catalyst as acetone palladium, diphenylphosphino ferrocene palladium etc., yield can be improved.
It is sub- that thus obtained diamines of the invention can be used as the polyimide precursors such as polyamic acid, poly amic acid ester, polyamides The raw material of amine, polyureas, polyamide etc. (these are referred to as " polymer ").The polymer is for example dissolvable in water defined organic molten It is used in agent as aligning agent for liquid crystal, but is not limited only to the purposes.Hereinafter, to including that diamines shown in formula [1] gathers in the structure Object is closed to be illustrated.
< polymer >
Polymer of the invention is obtained using the diamines of aforementioned present invention or derivatives thereof (being described below) , there is structure shown in the following formula [2] from diamine component.
(in formula [2], Y1For singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2It is each independently-H ,-OH ,=O or 1 Valence organic group, R3For the alkylidene of carbon atom number 1~3, * indicates the position with other group bondings.In addition, phenyl ring is any Hydrogen atom is optionally replaced by 1 valence organic group.)
As structure shown in the formula [2] for being originated from diamine component in the polymer, preferably there is structure shown in following formula [3].
(in formula [3], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Each independently For-H ,-OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3, * is indicated and other bases The position of group's bonding.In addition, any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.)
Herein, the derivative as aforementioned present invention diamines can be enumerated and is formed by connecting with 2 or more above-mentioned diamines Structure or by above-mentioned Y1、Y2Connect the diamines of structure made of above-mentioned diamines.In addition, other than the structure of above-mentioned formula [2], Structure from diamine component also may include the structure (being described below) from other diamines.
It should be noted that the alkylidene as 1 valence organic group, carbon atom number 1~3 in formula [2] and formula [3], it can It enumerates and formula [1] identical example.
In addition, polymer of the invention is preferably selected from containing following from the viewpoint of using as aligning agent for liquid crystal At least one of polyimide precursor and its imide compound, that is, polyimides of structural unit shown in formula [4].
(in formula [4], X1For the 4 valence organic groups from tetracarboxylic acid derivatives, W1For from formula [2] or formula [3] institute Show the divalent organic group of the diamines of structure.R5And R6Indicate the alkyl of hydrogen atom or carbon atom number 1~5, A1And A2It is respectively independent Ground indicates the alkynyl of hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~5 or carbon atom number 2~5.)
In formula [4], as the alkyl of carbon atom number 1~5, such as methyl, ethyl, n-propyl, isopropyl, just can be enumerated Butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, sec-amyl, tertiary pentyl etc.；As the alkenyl of carbon atom number 2~5, such as Can enumerate vinyl, allyl, 1- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 4- pentenyl etc.；As the alkynyl of carbon atom number 2~5, such as acetenyl, 1- propinyl, 2- propine can be enumerated Base (propargyl), 3- butynyl, pentynyl etc..Wherein, the viewpoint of the difficulty carried out from imidization reaction when heating goes out Hair, R5And R6It is preferred that hydrogen atom, methyl or ethyl, more preferable hydrogen atom or methyl.From the viewpoint of liquid crystal aligning, A1With A2It is preferred that hydrogen atom or methyl.
X1As long as being the 4 valence organic groups from tetracarboxylic acid derivatives, structure is not particularly limited.In addition, X1It can be with According to polymer dissolubility in a solvent, aligning agent for liquid crystal coating, be made liquid crystal orientation film when liquid crystal orientation, The degree of characteristic needed for voltage retention, stored charge etc. is suitably selected, and may exist a kind in same polymer, can also Two or more is deposited with mixed.
X1Tetracarboxylic dianhydride can be not only used, its tetracarboxylic acid derivatives, that is, tetrabasic carboxylic acid, tetrabasic carboxylic acid dihalo- can also be used Compound, tetracarboxylic acid acid dialkyl ester compound or tetracarboxylic acid acid dialkyl ester dihalide.As tetracarboxylic dianhydride or derivatives thereof, more It is preferable to use at least one kind of in tetracarboxylic dianhydride shown in following formula [6] or derivatives thereof.
In formula [6], V1For the 4 valence organic groups with ester ring type structure, structure is not particularly limited.As concrete example Son can enumerate following formula [V1- 1]~formula [V1-44]。
Formula [V1- 1]~formula [V1- 4] in, R7~R27It can be the same or different, it is former to be each independently hydrogen atom, halogen Son, the alkynyl of the alkyl of carbon atom number 1~6, the alkenyl of carbon atom number 2~6, carbon atom number 2~6, the carbon containing fluorine atom are former The 1 valence organic group or phenyl of subnumber 1~6.From the viewpoint of liquid crystal aligning, R7~R27It is preferred that hydrogen atom, halogen atom, first Base or ethyl, more preferable hydrogen atom or methyl.
As formula [V1- 1] specific structure can enumerate following formula [V1- 1-1]~formula [V1- 1-6] shown in structure.From liquid From the perspective of brilliant orientation and light reaction sensitivity, particularly preferred following formula [V1- 1-1] shown in structure.
In formula [4], W1As long as being the divalent organic group from the diamines with structure shown in formula [2] or formula [3], knot Structure is just not particularly limited, and can mix and deposit two or more.In addition, W1The structure of diamine component used in the corresponding present invention, contains There is the specific diamines with structure shown in formula [1] (for example, selected from by following formula [W1- 1]~formula [W1- 13] compound group shown in At group at least one kind of diamines).
It should be noted that formula [W1- 3] in, Boc indicates following shown groups (tert-butoxycarbonyl).
Wherein, W1Without all structures corresponding with above-mentioned diamines.Part W1May include with other than above-mentioned diamines The corresponding structure of diamines (other diamines).Structure (hereinafter referred to as " structure W corresponding with other diamines2") can be as follows It is generalized to state progress as shown in formula [7].It should be noted that as the A in following formula [7]1And A2, can enumerate and formula [4] identical example.
In addition, if to structure W shown in formula [7]2If being illustrated, then such as following formula [W2- 1]~formula [W2- 173] institute Show.
It should be noted that formula [W2- 168], formula [W2- 169], formula [W2- 172] and formula [W2- 173] the Boc group table in Show following shown tert-butoxycarbonyls.
When polyimide precursor containing structural unit shown in formula [4] contains structural unit shown in formula [7] simultaneously, relative to The total amount of formula [4] and formula [7], structural unit shown in formula [4] are preferably 10 moles of % or more, more preferably 20 moles of % or more, Particularly preferably 30 moles of % or more.
About the molecular weight of polyimide precursor, polyimides as Inventive polymers, by containing the polymer When aligning agent for liquid crystal obtains liquid crystal orientation film, it is contemplated that the operability when intensity of its film (liquid crystal orientation film), film formation And the uniformity of film, it is preferred to use GPC (gel permeation chromatography, Gel Permeation Chromatography) method measurement Weight average molecular weight be 2000~500000, more preferably 5000~300000, further preferably 10000~100000.
The manufacturing method > of < polymer
In the following, the main manufacture methods to Inventive polymers are illustrated.It should be noted that method described below For Production Example, it is not limited to that.
For example, this is poly- when the polymer containing structural unit shown in formula [4] is the polyamic acid as polyimide precursor Closing object can be obtained by the reaction of tetracarboxylic dianhydride and diamine component as tetracarboxylic acid derivatives.Polyamides is obtained by the reaction When amino acid, well known synthetic method can be used.The synthetic method is to make tetracarboxylic dianhydride and diamine component in organic solvent The method reacted.The advantages of this method is to be easier to carry out in organic solvent, and does not generate by-product.
As the organic solvent for above-mentioned reaction, as long as the organic molten of the polyamic acid (polymer) generated can be dissolved Agent is just not particularly limited, such as can enumerate n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- pyrroles Alkanone, N- ethyl-2-pyrrolidone, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy Base sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, Methylethyl The molten fibre of ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl Agent acetic acid esters, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol Single-butyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol (DEG), diglycol monotertiary acetic acid esters, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol list first Base ether, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol list second Acid esters list propyl ether, 3- methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, two Isopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, Propyl ether, hexyl ether, dioxanes, n-hexane, pentane, normal octane, Anaesthetie Ether, cyclohexanone, ethylene carbonate, carbonic acid are sub- Propyl ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ethylether, pyruvic acid Methyl esters, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy Base propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxyl -4- Methyl -2 pentanone, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- butoxy-N, N- Dimethylpropionamide etc..These substances can be used alone, and can also be used in mixed way.Even in addition, insoluble polyamic acid The solvent of (polymer), can also mix in above-mentioned organic solvent in the range of the polyamic acid of generation will not be precipitated makes With.In particular, the moisture in organic solvent hinders polymerization reaction, and then become the reason of polyamic acid generated hydrolyzes, therefore have Solvent preferably uses the organic solvent through dehydrating as far as possible.
When tetracarboxylic dianhydride and diamine component react in organic solvent, can enumerate stirring makes diamine component dispersion or molten The solution that solution obtains in organic solvent, directly add tetracarboxylic dianhydride or make its be dispersed or dissolved in organic solvent come into The method of row addition；In the side for making tetracarboxylic dianhydride be dispersed or dissolved in addition diamine component in solution obtained in organic solvent Method；Alternately addition tetracarboxylic dianhydride and the method for diamine component etc., can use any method therein.In addition, tetrabasic carboxylic acid When dianhydride or diamine component are made of multiple compounds, can be reacted in the state of being pre-mixed, can also respectively according to It is secondary to be reacted, the low-molecular weight that reacted respectively can also be subjected to hybrid reaction and form high molecular weight body.
Condensation temperature can choose the arbitrary temp in -20 DEG C~150 DEG C, preferably -5 DEG C~100 DEG C of range at this time.Separately Outside, polycondensation reaction can carry out under any concentration, but if concentration is too low, then be difficult to obtain the polymer of high molecular weight, if Excessive concentration, then the viscosity of reaction solution is excessively high, it is difficult to equably stir, therefore tetracarboxylic dianhydride and diamine component in reaction solution Total concentration is preferably set to the 1 mass % of mass %~50, is more preferably set as 5 mass of mass %~30 %.It can also be existed with initial reaction stage It is carried out under high concentration, adds organic solvent thereafter.
In the polymerization reaction of polyamic acid, the ratio between total mole number of the total mole number of tetracarboxylic dianhydride and diamine component (four Total mole number/diamine component total mole number of carboxylic acid dianhydride) it is preferably 0.8~1.2.It is identical as common polycondensation reaction, it should For molar ratio closer to 1.0, the molecular weight of the polyamic acid of generation is bigger.
When polymer containing structural unit shown in formula [4] is poly amic acid ester, tetracarboxylic acid acid diesters dichloride can be passed through Object is reacted with diamine component, or is reacted tetracarboxylic acid acid diesters and diamine component in the presence of suitable condensing agent or alkali and come It arrives.Or the carboxylate in amic acid can also be made using high molecular weight reactive by pre-synthesis polyamic acid in aforementioned manners Change to obtain.
Specifically, for example, can by making tetracarboxylic acid acid diesters dichloride and diamines in the presence of alkali and organic solvent, It is reacted 30 minutes~24 hours, preferably 1 hour~4 hours at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C and carrys out synthesizing polyamides Acid esters.
As alkali, pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used, but in order to react mild progress, preferably For pyridine.From the viewpoint of for the amount easily removed and being easy to get high molecular weight body, relative to tetracarboxylic acid acid diesters dichloro Compound, the additive amount of alkali are preferably 2 times moles~4 times moles.
In addition, making tetracarboxylic acid acid diesters and diamine component in the presence of condensing agent when polycondensation, as alkali, triphenyl can be used Phosphite ester, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl two Imidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea four Borofluoride, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea hexafluorophosphate, the (thio -3- of 2,3- dihydro -2- Benzoxazolyl) phosphonic acid diphenyl ester, 4- (4,6- dimethoxy -1,3,5- triazine -2- base) 4- methoxyl group morpholine hydrochloride n hydration Object etc..
In addition, being stated in the method for condensing agent in use, by addition lewis acid as additive, reaction can be efficiently It carries out.As lewis acid, the preferably lithium halides such as lithium chloride, lithium bromide.Relative to the diamines or tetracarboxylic acid acid diesters reacted, Lewis acidic additive amount is preferably 0.1 times of mole~1.0 times mole.
The solvent used in above-mentioned reaction, can using with the solvent phase that is used when above-mentioned shown synthesizing polyamides acid With solvent carry out, but from the dissolubility of monomer and polymer, preferably n-methyl-2-pyrrolidone, gamma-butyrolacton, They can be used a kind or mix two or more come using.Concentration when about synthesis, from the precipitation for being not susceptible to polymer and It is easy to get from the perspective of high molecular weight body, the tetrabasic carboxylic acids such as tetracarboxylic acid acid diesters dichloride, tetracarboxylic acid acid diesters in reaction solution The total concentration of the derivative and diamine component preferably 1 mass mass of %~30 %, the more preferable 5 mass mass of %~20 %.In addition, being The hydrolysis of tetracarboxylic acid acid diesters dichloride is prevented, solvent used in the synthesis of poly amic acid ester is preferably dehydrated as far as possible, excellent It is selected in nitrogen atmosphere, extraneous gas is prevented to be mixed into.
When polymer containing structural unit shown in formula [4] is polyimides, to have formula [2] or formula [3] institute in main chain Show the substance of divalent group, can be obtained by making above-mentioned polyamic acid dehydration closed-loop.In the polyimides, amide acidic group Dehydration closed-loop rate (acid imide rate) is not necessarily to be 100%, can depending on the application or purpose arbitrarily adjusts.
As the method for making polyamic acid imidizate, the hot acid imide for directly heating polyamic acid solution can be enumerated Change, catalysis imidizate of addition catalyst etc. in polyamic acid solution.
Make 100 DEG C~400 DEG C of temperature when polyamic acid hot-imide in the solution, preferably 120 DEG C~250 DEG C, preferably outside the water exclusion system that will be generated by imidization reaction while carry out hot-imide.
The catalysis imidizate of polyamic acid can by adding basic catalyst and acid anhydrides in polyamic acid solution, - 20 DEG C~250 DEG C, preferably stir and carry out at 0 DEG C~180 DEG C.The amount of basic catalyst is 0.5 mole of amide acidic group Times~30 moles times, preferably 2 moles times~20 moles times, the amount of acid anhydrides is 1 mole times~50 moles times of amide acidic group, excellent It is selected as 3 moles times~30 moles times.As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine can be enumerated Deng, wherein pyridine has appropriate alkalinity for carrying out reaction, thus preferably.As acid anhydrides, can enumerate acetic anhydride, Trimellitic anhydride, pyromellitic dianhydride etc., wherein it is easy to carry out purifying after reaction when using acetic anhydride, thus preferably. It can be controlled by adjusting catalytic amount and reaction temperature, reaction time based on the acid imide rate of catalysis imidizate.
In addition, promote dealcoholysis to make its closed loop as described above, by heating poly amic acid ester at high temperature, it can also To obtain polyimides.
It should be noted that from the polyimide precursors such as polyamic acid, poly amic acid ester or the reaction solution of polyimides When the middle polyamic acid for recycling generation, poly amic acid ester, polyimides, reaction solution, which is put into poor solvent, makes its precipitating ?.As the poor solvent for precipitating, methanol, acetone, hexane, butyl cellosolve, heptane, Methylethyl can be enumerated Ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..Put into the polyimide precursor precipitated in poor solvent or poly- Acid imide can be dried in room temperature or heating under normal or reduced pressure after being recovered by filtration.In addition, if repeat into Row 2~10 times polyimide precursors for recycling precipitating or polyimides are re-dissolved in the behaviour of organic solvent and reprecipitation recycling Make, then can reduce the impurity in polymer.As poor solvent at this time, such as alcohols, ketone, hydrocarbon can be enumerated etc., such as Fruit is using 3 kinds or more the poor solvents in these solvents, then purification efficiency further increases, so it is preferred that.
Thus obtained polymer of the invention is soluble in defined organic solvent and uses as aligning agent for liquid crystal. The aligning agent for liquid crystal is the liquid crystal orientation film for indicating to control the liquid crystal molecular orientation of liquid crystal layer in element in liquid crystal.With Under, the aligning agent for liquid crystal containing polymer of the invention is illustrated.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the invention contains the polymer obtained by diamine component, which includes to have from upper State the diamines of structure shown in the formula [2] of diamine component.In addition, the aligning agent for liquid crystal, which preferably comprises to have, is originated from above-mentioned diamine component Formula [3] shown in structure polymer.In addition, the polymer is preferably selected from the Asia of the polyamides containing structural unit shown in formula [4] At least one of amine precursor and its imide compound, that is, polyimides.
Wherein, the polymer contained in aligning agent for liquid crystal of the invention can with all polymer of the invention, in addition, Two or more different polymer of structure in Inventive polymers can be contained in the limit for playing effect of the present invention.Or Person can also contain other polymer, that is, not have divalent base shown in formula [2] or formula [3] in addition to the polymers of the present invention The polymer of group.As the type of other polymer, polyamic acid can be enumerated, polyimides, poly amic acid ester, polyester, gathered Amide, polyureas, polysiloxane, cellulose derivative, polyacetals, polystyrene or derivatives thereof, poly- (styrene-phenyl Maleimide) derivative, poly- (methyl) acrylate etc..
Inventive polymers when aligning agent for liquid crystal of the invention contains other polymer, relative to whole component of polymer Ratio be preferably 5 mass % or more, as one example of which, 5 mass of mass %~95 % can be enumerated.The present invention is poly- The ratio for closing object can suitably be selected according to the characteristic of aligning agent for liquid crystal or liquid crystal orientation film.
Aligning agent for liquid crystal of the invention is for making liquid crystal orientation film, from the viewpoint of forming uniform film, generally Using the form of coating fluid.Aligning agent for liquid crystal of the invention preferably also contain aforementioned polymer ingredient and dissolve the polymer at The coating fluid of the organic solvent divided.At this point, the concentration of the polymer in aligning agent for liquid crystal can according to film to be formed The setting of thickness and suitably change.From the viewpoint of forming uniform and flawless film, preferably 1 mass % or more, from From the perspective of the storage stability of solution, it is preferably set to 10 mass % or less.The concentration of particularly preferred polymer is 2 matter Measure the mass of %~8 %.
About the organic solvent contained in aligning agent for liquid crystal of the invention, do not have as long as the organic solvent of dissolution polymer It is particularly limited to.It is sub as its concrete example, n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2- can be enumerated Pyrrolidones, N- ethyl-2-pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, Methylethyl Ketone, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanone etc..Wherein, it is preferred to use n-methyl-2-pyrrolidone, N- second Base -2-Pyrrolidone, gamma-butyrolacton.It should be noted that organic solvent listed herewith, which can be used alone, to be mixed It uses.Moreover, even the solvent of insoluble polymer can also be mixed into the range of the polymer of generation will not be precipitated It is used in organic solvent.
In addition, for the organic solvent contained in aligning agent for liquid crystal, it is generally used on the basis of above-mentioned solvent and with mentioning Mixed solvent made of the solvent of the surface smoothness of coating, film when high coating of liquid crystalline alignment agent, liquid crystal of the invention It is also preferred that using such mixed solvent in alignment agent.The specific example for the organic solvent being listed below, but it is not limited to this A little examples.
Such as ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- can be enumerated Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- Methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycol, dipropyl ether, dibutyl ethers, hexyl ether, dioxanes, ethylene glycol dimethyl ether, ethylene glycol diethyl Ether, ethylene glycol dibutyl ethers, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl- 2 pentanone, diethylene glycol (DEG) methyl ethyl ether, diethylene glycol dibutyl ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- Ethoxybutyl acetic acid esters, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol list Acetic acid esters, ethylene acetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl Ether, ethylene glycol list isoamyl ether, ethylene glycol mono hexyl ether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol (DEG), propylene glycol, propylene glycol list Butyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol single methyl ether acetic acid esters, ethylene glycol Single monoethyl ether acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol acetate, ethylene acetate, diglycol monotertiary second Base ether acetic acid ester, diethylene glycol monobutyl ehter acetic acid esters, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol (DEG) acetic acid esters, three Glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid are just Butyl ester, propyleneglycolmethyletheracetate list ethylether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid first Base ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl Acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate equal solvent.
In addition, such as solvent shown in following formula [S-1]~formula [S-3] can be used in addition to above-mentioned solvent.
In formula [S-1] and formula [S-2], R28And R29Indicate the alkyl of carbon atom number 1~3.Alkane as carbon atom number 1~3 Base, such as methyl, ethyl, n-propyl, isopropyl can be enumerated etc..In addition, in formula [S-3], R30Indicate carbon atom number 1~4 Alkyl.As the alkyl of carbon atom number 1~4, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl can be enumerated Base, sec-butyl, tert-butyl etc..
Organic solvent in, it is preferred to use 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, propylene glycol list Butyl ether, diethylene glycol diethyl ether, 4- hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. The type and content of the solvent can suitably be selected according to apparatus for coating, application conditions, coating environment of aligning agent for liquid crystal etc..
In addition, these solvents are preferably 20 mass of mass %~99 % of the entirety of solvent contained by aligning agent for liquid crystal.Wherein, excellent Select 20 mass of mass %~90 %.More preferably 20 mass of mass %~70 %.
Aligning agent for liquid crystal of the invention within the scope of the effect of the invention, can also add containing except polymer at Point and organic solvent other than ingredient.As the addition ingredient, can enumerate for improving the closely sealed of liquid crystal orientation film and substrate Property, the adaptation of liquid crystal orientation film and sealing material closely sealed auxiliary agent, the crosslinking agent for improving liquid crystal aligning film-strength, be used for Adjust the dielectric constant of liquid crystal orientation film, the dielectric of resistance, conductive materials etc..These specific examples for adding ingredient are such as related to Disclosed in each known document of aligning agent for liquid crystal like that, if it have to give one example, International Publication No. can be enumerated Ingredient disclosed in [0105] of No. 2015/060357 bulletin~[0116] section etc..
< liquid crystal orientation film >
Liquid crystal orientation film of the invention is obtained by above-mentioned aligning agent for liquid crystal.Liquid crystal is obtained by aligning agent for liquid crystal if enumerating One example of the method for alignment films, can enumerate and the aligning agent for liquid crystal of coating fluid form is applied on substrate, dry, roasting And film is obtained, implement the method for orientation process to the film by brushing facture or light orientation position logos.
As the substrate for being coated with aligning agent for liquid crystal of the invention, it is not particularly limited as long as the high substrate of the transparency, Glass substrate, silicon nitride board can be used, and the plastic bases such as acrylic compounds substrate, polycarbonate substrate also can be used Deng.At this point, if using the ITO electrode being formed with for driving liquid crystal etc. substrate, from the viewpoint of technique simplify be preferred 's.In addition, the liquid crystal of reflection-type indicates in element, it is opaque that Silicon Wafer etc. also can be used if only forming unilateral substrate The material of the reflected lights such as aluminium also can be used in substrate, electrode at this time.
The coating method of aligning agent for liquid crystal is not particularly limited, industrially, silk-screen printing, hectographic printing, soft version Printing, ink-jet method etc. are common.As other coating methods, there is infusion process, rolling method, slot coated method, spin-coating method, is sprayed Method etc. can use these methods according to purpose.
Roasting after aligning agent for liquid crystal is coated on substrate can pass through heating plate, recirculation furnace, infrared heating heating furnace etc. Heating unit carries out at 50 DEG C~300 DEG C, preferably 80 DEG C~250 DEG C, evaporates solvent, is formed film (liquid crystal orientation film). It is unfavorable in terms of the power consumption that liquid crystal indicates element if the thickness of the film formed after roasting is blocked up；If excessively thin, sometimes Liquid crystal indicates that the reliability of element reduces, therefore preferably 5nm~300nm, more preferably 10nm~100nm.Liquid crystal level takes To or when tilted alignment, the film after roasting can be irradiated by brushing or polarized UV rays etc. be handled.
On substrate after coating of liquid crystalline alignment agent, added by heating plate, thermal cycle type baking oven, IR (infrared ray) type baking oven etc. Hot cell evaporation solvent simultaneously roasts.Drying, calcining process after coating of liquid crystalline alignment agent can choose arbitrary temperature and time. It is sufficiently removed generally for by contained solvent, can enumerate and roast 1 minute~10 minutes at 50 DEG C~120 DEG C, then 5 minutes~120 minutes conditions are roasted at 150 DEG C~300 DEG C.
The liquid crystal that liquid crystal orientation film of the invention is suitable as the Transverse electric-field types such as IPS mode, FFS mode indicates element Liquid crystal orientation film, particularly suitable as FFS mode liquid crystal indicate element liquid crystal orientation film.
< liquid crystal indicates element >
Liquid crystal of the invention indicates that element has above-mentioned liquid crystal orientation film, is obtained obtaining to have by above-mentioned aligning agent for liquid crystal Liquid crystal orientation film substrate after, make liquid crystal cells by known method, use the liquid crystal cells formed element.Citing and Speech is that the liquid crystal for having liquid crystal cells indicates that there are 2 of relative configuration to be arranged between substrate, substrate for element, the liquid crystal cells Liquid crystal layer and substrate and liquid crystal layer between the liquid crystal orientation film formed by aligning agent for liquid crystal of the invention that is arranged.
As the substrate for indicating element for liquid crystal of the invention, do not limited especially as long as the high substrate of the transparency It is fixed, but the substrate for driving the transparent electrode of liquid crystal is usually formed on substrate.As specific example, can enumerate with it is upper State the identical substrate of the substrate recorded in liquid crystal orientation film.
In addition, liquid crystal orientation film is roasted and shape after aligning agent for liquid crystal of the invention is coated on the substrate At, detailed content is as described above.
Constituting liquid crystal of the present invention indicates that the liquid crystal material of the liquid crystal layer of element is not particularly limited, and can enumerate nematic liquid Positive type liquid crystal material, any in negative type liquid crystal material can be used wherein it is preferred that nematic crystal in brilliant and smectic crystal Person.Specifically, MLC-2003, MLC-6608, MLC-6609, MLC-3019, MLC- of Merck & Co., Inc. can be used for example 2041, MLC-7026-100 etc..
Specifically, prepare the substrate of transparent glass system, be arranged on a substrate common electrode, another substrate it Upper setting segment electrode.These electrodes can be for example ITO electrode, and carry out being patterned so as to can be realized desired figure As display.Then insulating film is set to cover in a manner of common electrode and segment electrode on each substrate.Insulating film such as can be with It is utilization sol-gel method formation by SiO2-TiO2The film of formation.Then, under the conditions of above-mentioned, the shape on each substrate At liquid crystal orientation film.
Then, for example ultra-violet solidified sealing material is configured to one in two substrates for being formed with liquid crystal orientation film The specified position on substrate is opened, further after several specified positions configuration liquid crystal in liquid crystal aligning film surface, by with liquid The opposite form of brilliant alignment films crimps the fitting of another substrate, sprawls liquid crystal on liquid crystal orientation film front, then right The whole surface irradiation ultraviolet light of substrate solidifies sealing material, to obtain liquid crystal cells.
Alternatively, specified position on a substrate configures as liquid crystal orientation film subsequent process is formed on substrate When sealing material, preset can from the opening portion of external filling liquid crystal, in the case where not configuring liquid crystal adhesive substrates it Afterwards, liquid crystal material is injected in liquid crystal cells by the opening portion of setting on the sealing material, then seals this with bonding agent and opens Oral area is to obtain liquid crystal cells.Vacuum impregnation can be used in the injection of liquid crystal material, also can be used and utilizes in an atmosphere The method of capillarity.
In above-mentioned any means, in order to ensure the space of the filling liquid crystal material in liquid crystal cells, preferably take as follows Means: being arranged columnar protrusion on a substrate, between perhaps spreading spacer on a substrate or being mixed into sealing material Parting, or by they combine etc..
Then, the setting of polarizing film is carried out.Specifically, it is preferable that in the face stickup with liquid crystal layer opposite side of 2 substrates A pair of of polarizing film.
It should be noted that as long as liquid crystal orientation film of the invention and liquid crystal indicate element using liquid crystal aligning of the invention Agent is not just limited by above-mentioned record, can also be using other well known method production.Such as Japanese Unexamined Patent Publication 2015-135393 Many documents such as [0074] of bulletin~[0081] section all disclose until obtaining liquid crystal by aligning agent for liquid crystal indicates element Process.
Indicate that component reliability is excellent using the liquid crystal that aligning agent for liquid crystal of the invention makes as shown above, suitable for big Screen high-definition liquid crystal TV etc..
Embodiment
The detail of manufacturing method of the present invention is illustrated hereinafter, enumerating embodiment etc., which is to raw material Composition, the test method studied of proportion and its result and exemplary manufacturing method, but the present invention is not implemented by these The restriction of example.
It should be noted that the abbreviation and evaluating characteristics of compound, solvent are as described below.
< organic solvent >
NMP:N- N-methyl-2-2-pyrrolidone N
NEP:N- ethyl-2-pyrrolidone
GBL: gamma-butyrolacton
BCS: butyl cellosolve
PB: glycol monobutyl ether
DME: dipropylene glycol dimethyl ether
DAA:4- hydroxy-4-methyl-2-pentanone
DEDG: diethylene glycol diethyl ether
DIBK:2,6- valerone
DIPE: Di Iso Propyl Ether
DIBC:2,6- 2,6-dimethyl-4-heptanol
Pd/C: palladium carbon
DMSO: dimethyl sulfoxide
THF: tetrahydrofuran
< additive >
LS-4668:3- epoxy propoxy propyl triethoxysilane
LS-3150:3- aminopropyltriethoxywerene werene
<1The measurement > of H-NMR
Device: Varian NMR system 400NB (400MHz) (Varian corporation) and JMTC-500/54/SS (500MHz) (JEOL corporation)
Measure solvent: CDCl3(deuterated chloroform), DMSO-d6(deuterated dimethyl sulfoxide)
Primary standard substance: TMS (tetramethylsilane) (δ: 0.0ppm,1) and CDCl H3(δ: 77.0ppm,13C)
The molecular weight measurement > of < polyimide precursor and imide amination polymer
Using room temperature gel permeation chromatography (GPC) device (GPC-101) (Showa electrician corporation) and column (KD-803, KD- 805) (Shodex corporation), measures under the following conditions.
Column temperature: 50 DEG C
Eluent: N, N'- dimethylformamide are (as additive, lithium bromide monohydrate (LiBrH2O) it is 30mmol/L (liter), phosphoric acid anhydrous crystalline (orthophosphoric acid) are 30mmol/L, and tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minutes
Calibration curve production standard sample: TSK standard polyethylene oxide (molecular weight；About 900000,150000, 100000 and 30000, Tosoh corporation) and polyethylene glycol (molecular weight；About 12000,4000 and 1000, Polymer Laboratory Company (Port リ マ ー ラ ボ ラ ト リ ー society) system)
The measurement > of < viscosity
Aftermentioned synthesis example and compare in synthesis example, the viscosity of polyamic acid solution uses E type viscosimeter TVE-22H (eastern machine Industry companies' system), it is measured at sample size 1.1mL, cone rotor TE-1 (1 ° 34 ', R24).
The synthesis > of < diamine compound (DA-1)
BNPU (50g, 140mmol), potassium carbonate (44.4g, 320mmol) and NMP are put into 2L (liter) four-hole boiling flask (1000g) is warming up to 50 DEG C under blade stirring, 40% glyoxal water solution (46.7g, 320mmol) is instilled in 10 minutes, Stirring 12 hours.Remain raw material in HPLC (high performance liquid chromatography), thus further be added potassium carbonate (44.4g, 320mmol) and 40% glyoxal water solution (46.7g, 320mmol), stirring obtain compound [A] in 12 hours.Confirmation raw material disappears After mistake, salt is filtered, is instilled sulfuric acid (15g), after keeping solution acid, is stirred 24 hours at 70 DEG C.Confirmed with HPLC and is reacted After, methanol (1000g), pure water (1000g) is added, is stirred 1 hour after being cooled to 5 DEG C.The crystal of precipitation is filtered under diminished pressure, It after being cleaned with methanol (100g), is dried, obtains powder crystal (compound [B]) (yield 41.7g, yield 76%).
1H-NMR (DMSO-d6): 8.18-8.10 (4H, m), 7.56-7.50 (2H, m), 7.45-7.39 (2H, m), 3.95 (2H, s), 3.62-3.55 (4H, m), 2.97-2.91 (4H, m)
Under the conditions of pressurized with hydrogen, by obtained compound [B] (35g, 87.8mmol), (50% is aqueous by 5 mass %Pd/C Type), the mixture of characteristic egression active carbon (3.5g) and dioxanes (350g) stirs 8 hours at 60 DEG C.After reaction, Filtration catalytic agent, is then concentrated, and is added 2- propyl alcohol (350g), is stirred 1 hour at 5 DEG C.The crystal of precipitation was depressurized Filter, after being cleaned with 2- propyl alcohol (70g), is dried, obtains powder crystal DA-1 (yield 27g, yield 92%).
1H-NMR (DMSO-d6): 6.87-6.84 (2H, m), 6.81-6.77 (2H, m), 6.51-6.46 (4H, m), 4.90 (4H, s), 3.79 (2H, s), 3.45-3.38 (4H, m), 2.62-2.57 (4H, m)
[synthesis example 1]
In the four-hole boiling flask of the 100mL with agitating device and with nitrogen ingress pipe, the DA-1 that is added (3.38g, After 10.0mmol), NMP28.8g is added, is stirred and makes it dissolve when being sent into nitrogen.While stirring the solution, CA-1 is added in side After (0.87g, 4.0mmol), CA-2 (1.08g, 5.5mmol) and NMP 9.6g, further stirring 12 is small under the conditions of 50 DEG C When, thus obtain polyamic acid solution shown in following table 1 (PAA-A1).
[2~synthesis example of synthesis example 5]
Using diamine component shown in following table 1, tetracarboxylic acid sour component and NMP (n-methyl-2-pyrrolidone), make it respectively It is carried out similarly implementation with synthesis example 1, thus obtains polyamic acid solution shown in following table 1 in addition to this for reaction temperature (PAA-A2) and polyamic acid solution (PAA-B1)~(PAA-B3).
[table 1]
[Examples 1 to 10 and Comparative Examples 1 and 2]
Solvent and additive are added while stirring by polyamic acid solution is obtained in 1~synthesis example of synthesis example 5, so as to obtain Aligning agent for liquid crystal in solvent be composition shown in following table 2 and following Table 3, and then be stirred at room temperature 2 hours, thus distinguish Obtain aligning agent for liquid crystal.
[table 2]
Embodiment Polymer※1 Additive※2 Solvent ratio※3
1 PAA-A1(100) LS-4668(1) NMP (71), BCS (25)
2 PAA-A2 (40), PAA-B1 (60) LS-3150(1) NMP (76), BCS (20)
3 PAA-A1(100) LS-4668(1) NMP (46), GBL (30), BCS (20)
4 PAA-A1(100) LS-4668(1) NMP (46), GBL (30), PB (20)
5 PAA-A1(100) LS-4668(1) NMP (46), GBL (30), DME (20)
6 PAA-A1(100) LS-4668(1) NMP (46), GBL (30), DAA (10), DEDG (10)
7 PAA-A1(100) LS-4668(1) NMP (41), GBL (30), PB (15), DIBK (10)
8 PAA-A1(100) LS-4668(1) NMP (41), GBL (30), PB (15), DIPE (10)
9 PAA-A1(100) LS-4668(1) NMP (41), GBL (30), PB (15), DIBC (10)
10 PAA-A1(100) LS-4668(1) NMP (46), NEP (30), PB (20)
※ 1: indicate each polymer phase for the import volume (parts by weight) of whole 100 parts by weight of polymer.
※ 2: import volume (parts by weight) of each additive relative to whole 100 parts by weight of polymer is indicated.
※ 3: import volume (parts by weight) of the solvent relative to 100 mass parts of aligning agent for liquid crystal is indicated.
[table 3]
Comparative example Polymer※1 Additive ※ 2 Solvent ratio※3
1 PAA-B2(100) LS-4668(1) NMP (71), BCS (25)
2 PAA-B3 (40), PAA-B1 (60) LS-3150(1) NMP (76), BCS (20)
※ 1: indicate each polymer phase for the import volume (parts by weight) of whole 100 parts by weight of polymer.
※ 2: import volume (parts by weight) of each additive relative to whole 100 parts by weight of polymer is indicated.
※ 3: import volume (parts by weight) of the solvent relative to 100 mass parts of aligning agent for liquid crystal is indicated.
It should be noted that 1~※ of ※ 3 in table 2 and table 3 is as follows.
※ 1: indicate each polymer phase for the import volume (parts by weight) of whole 100 parts by weight of polymer.
※ 2: import volume (parts by weight) of each additive relative to whole 100 parts by weight of polymer is indicated.
※ 3: import volume (parts by weight) of the solvent relative to 100 mass parts of aligning agent for liquid crystal is indicated.
<production that the liquid crystal based on brushing method indicates element>
Prepare having a size of 30mm × 35mm and with a thickness of the electroded glass substrate of 0.7mm.On substrate, as the 1st Layer is formd for constituting opposite electrode and having the IZO electrode of solid shape pattern.On the 1st layer of opposite electrode, as 2 layers, form SiN (silicon nitride) film to form a film using CVD method.The film thickness of 2nd layer of SiN film is 500nm, is asked as layer Insulating film and function.On the 2nd layer of SiN film, as the 3rd layer, the comb teeth-shaped picture for forming IZO film figure is configured Plain electrode, to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel is the vertical horizontal 5mm of 10mm.At this point, the 1st The opposite electrode of layer is in be electrically insulated with the 3rd layer of pixel electrode because of the effect of the 2nd layer of SiN film.
The pixel electrode of 3rd floor has in Japanese Unexamined Patent Publication 2014-77845 bulletin shown in the figure (Fig. 3) recorded, is multiple The comb teeth-shaped shape that " く " shape electrode member that center portion bends is arranged to make up.The width of the width direction of each electrode member Degree is 3 μm, between electrode member between be divided into 6 μm.It is formed " く " that the pixel electrode of each pixel is bent by multiple center portions Shape electrode member is arranged to make up, therefore the shape of each pixel not instead of oblong-shaped, is had in the same manner as electrode member in Shape that centre part bends, " く " similar to runic.Also, each pixel is using the bending part in the center as in boundary Lower segmentation, the 2nd region with the 1st region and downside on the upside of bending part.
If the 1st region of each pixel and the 2nd region are compared, the electrode member of their pixel electrode is constituted It is different to form direction.That is, using the brushing direction of aftermentioned liquid crystal orientation film as benchmark in the case where, the 1st region of pixel with The mode for the angle (clockwise) that the electrode member of pixel electrode is+10 ° is formed, and the 2nd region of pixel is with the electricity of pixel electrode The mode for the angle (counterclockwise) that pole element is -10 ° is formed.In addition, the 1st region of each pixel and the 2nd region are to pass through pixel Voltage between electrode and opposite electrode applies and the side of the spinning movement (converting in face) in real estate of the liquid crystal of induction It is constituted to the mode for being mutual reverse direction.
Then, after filtering aligning agent for liquid crystal with 1.0 μm of filter, it is spun on above-mentioned electroded substrate and conduct respectively Counter substrate is overleaf formed with ito film and has on glass substrate of the height for 4 μm of column spacer.Then at 80 DEG C Drying after five minutes, roasts 20 minutes at 230 DEG C, the polyimide film of film thickness 60nm is obtained on each substrate in heating plate.? On the polyimides film surface, pressure is pressed into roller diameter 120mm, roller revolving speed 500rpm, platform movement speed 30mm/ seconds, brushing cloth Under conditions of 0.3mm, after implementing brushing processing using rayon cloth, 1 minute ultrasonic irradiation is carried out in pure water, at 80 DEG C It is 10 minutes dry.
Using 2 kinds of substrates with above-mentioned liquid crystal orientation film, is combined, reserved in a manner of antiparallel with respective brushing direction Liquid crystal injecting port seals surrounding, and 3.8 μm of dummy cell is divided between production unit.The vacuum impregnating in the dummy cell at normal temperature After entering liquid crystal (Merck & Co., Inc.'s system, MLC-3019), inlet is sealed, the liquid crystal cells of antiparallel orientations are formed.Gained liquid crystal Unit, which constitutes FFS mode liquid crystal, indicates element.Later, liquid crystal cells are heated 1 hour at 120 DEG C, is used for after placing a Dinner Evaluation.
< just drive after flicker level evaluation >
The liquid crystal cells made are set to be become between 2 polarizing films that orthogonal mode configures with polarization axle, Without LED backlight is lighted in the state of application voltage, least way is become with the brightness of transmitted light, adjusts matching for liquid crystal cells Angle setting degree.Then, while the liquid crystal cells are applied with the alternating voltage of frequency 30Hz, side measures V-T curve, and (voltage-transmission rate is bent Line), the alternating voltage that relative transmittance is 23% is calculated as driving voltage.
In the measurement of flicker level, temporarily extinguishes the LED backlight lighted and light LED again after shading is placed 72 hours Backlight applies the alternating voltage for the frequency 30Hz that relative transmittance is 23% while starting to light backlight, makes liquid crystal Unit drives 60 minutes, tracking flashing amplitude.Flashing amplitude be will transmit through 2 polarizing films and its between liquid crystal cells LED The transmitted light of backlight is converted by the data collection/data logger connected by photodiode with I-V switching amplifier What unit 34970A (Agilent Technologies corporation) was read.Flicker level is calculated by following formula [8].
Flicker level (%)=× 100 [8] { flashing amplitude/(2 × z) }
In formula [8], z be will be by relative transmittance 23%, the driving of the alternating voltage of frequency 30Hz when brightness use The value that data collection/data logger converting unit 34970A is read.
Evaluation for blinking characteristic, from LED backlight and application alternating voltage start time is lighted to by 60 minutes Until, the case where flicker level is maintained less than 3% defines and is evaluated as "○" (to be less likely to occur to dodge after just starting driving Bright variation), the situation that flicker level in 60 minutes reaches 3% or more is defined and is evaluated as "×" and (is held after just starting driving Flashing variation easily occurs).
Moreover, it is 23 DEG C of state that the evaluation of the flicker level carried out according to the method described above, which is in the temperature of liquid crystal cells, It is carried out under the conditions of temperature.
< evaluation result >
It, will among the above for using the liquid crystal of each aligning agent for liquid crystal of above-described embodiment 1,2 and Comparative Examples 1 and 2 to indicate element The result of the evaluation of the ghost extinction time of implementation and the evaluation of the flicker level after just driving is shown in following table 4.
[table 4]
Flashing variation (%)
Embodiment 1 Zero (< 1)
Embodiment 2 ○(2.6)
Comparative example 1 ×(8.4)
Comparative example 2 ×(6.8)
As shown in Table 4, indicate that element is just starting to drive using the liquid crystal of the aligning agent for liquid crystal of embodiment 1 and embodiment 2 It is less likely to occur flashing variation after dynamic.
Industrial availability
Indicating that element can be made using the liquid crystal of the aligning agent for liquid crystal production obtained by diamines of the invention can reduce just The liquid crystal display device of flashing variation after just starting driving, may be suitably used to the expression of TN (Twisted Nematic) liquid crystal Element, stn liquid crystal indicate that element, TFT liquid crystal indicate that element, VA liquid crystal indicate that element, IPS liquid crystal indicate element, OCB (Optically self-Compensated Birefringence) liquid crystal indicates the expression member based on various modes such as element Part.

Claims (7)

1. a kind of diamines, which is characterized in that it is indicated by following formula [1],
In formula [1], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Be each independently-H ,- OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3, in addition, any hydrogen of phenyl ring is former Son is optionally replaced by 1 valence organic group.
2. a kind of polymer, which is characterized in that it is obtained as the diamine component comprising the diamines with structure shown in following formula [2] It arrives,
In formula [2], Y1For singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Being each independently-H ,-OH ,=O or 1 valence has Machine group, R3For the alkylidene of carbon atom number 1~3, * indicates the position with other group bondings, in addition, any hydrogen of phenyl ring is former Son is optionally replaced by 1 valence organic group.
3. polymer according to claim 2, which is characterized in that it is as comprising with structure shown in following formula [3] What the diamine component of diamines obtained,
In formula [3], Y1And Y2It is each independently singly-bound ,-O- ,-S- ,-COO- or-OCO-, R1And R2Be each independently-H ,- OH ,=O or 1 valence organic group, R3And R4It is each independently the alkylidene of carbon atom number 1~3, * is indicated and other group bondings Position, in addition, any hydrogen atom of phenyl ring is optionally replaced by 1 valence organic group.
4. polymer according to claim 2 or 3, which is characterized in that it is selected from containing structure list shown in following formula [4] At least one of polyimide precursor and its imide compound, that is, polyimides of member,
In formula [4], X1For the 4 valence organic groups from tetracarboxylic acid derivatives, W1For from structure shown in formula [2] or formula [3] Diamines divalent organic group, R5And R6Indicate the alkyl of hydrogen atom or carbon atom number 1~5, A1And A2It each independently represents Hydrogen atom, the alkyl of carbon atom number 1~5, the alkenyl of carbon atom number 2~5 or carbon atom number 2~5 alkynyl.
5. a kind of aligning agent for liquid crystal contains polymer and organic solvent described in any one of claim 2~4.
6. a kind of liquid crystal orientation film, which is characterized in that it is that the aligning agent for liquid crystal as described in claim 5 obtains.
7. a kind of liquid crystal indicates element, which is characterized in that have liquid crystal orientation film as claimed in claim 6.
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